WO2015155737A1 - Système et procédé destinés à la production de polycarbonates de divers poids moléculaires à en masse fondue - Google Patents

Système et procédé destinés à la production de polycarbonates de divers poids moléculaires à en masse fondue Download PDF

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WO2015155737A1
WO2015155737A1 PCT/IB2015/052605 IB2015052605W WO2015155737A1 WO 2015155737 A1 WO2015155737 A1 WO 2015155737A1 IB 2015052605 W IB2015052605 W IB 2015052605W WO 2015155737 A1 WO2015155737 A1 WO 2015155737A1
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polycarbonate
molecular weight
carbonate
catalyst
polymerization
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PCT/IB2015/052605
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English (en)
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Ignacio Vic Fernandez
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Sabic Global Technologies B.V.
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Priority to US15/111,271 priority Critical patent/US20170015784A1/en
Priority to CN201580012057.6A priority patent/CN106068295B/zh
Priority to KR1020167029663A priority patent/KR102165343B1/ko
Priority to EP15725880.7A priority patent/EP3129423B1/fr
Publication of WO2015155737A1 publication Critical patent/WO2015155737A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/42—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/205—General preparatory processes characterised by the apparatus used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C08G64/307—General preparatory processes using carbonates and phenols

Definitions

  • This application relates to a system and process for making melt
  • polycarbonate and especially relates to a system and process for making a variety of molecular weights of melt polycarbonate.
  • a continuous melt polymerization plant requires the adjustment of many polymerization parameters.
  • a high molecular weight polycarbonate is prepared under conditions of higher temperature and higher residence time as compared to a lower molecular weight polycarbonate. Accordingly, when switching from one molecular weight polycarbonate to another molecular weight polycarbonate, the following parameters are changed: molar ratio of the carbonate source to the dihydroxy monomer, the reaction temperatures in the oligomerization reactors, reaction temperatures in the polymerization reactors, the amount of alpha catalyst, and the overall throughput of the plant (residence time).
  • This changeover can take several hours, where, during the several hour changeover from one molecular weight polycarbonate to another molecular weight polycarbonate, a large amount of waste polycarbonate is produced.
  • This problem is increasingly an issue as the size of melt polymerization plants increases. For example, in a large melt polymerization plant that produces greater than 100,000 tons per year (t/y), a large amount of waste is undesirably produced during a changeover. As a result, the development of larger polycarbonate plants is hampered by the inefficiencies of the changeover process.
  • a melt polymerization process comprises melt
  • a catalyst composition comprises an alkali catalyst and/or a quaternary catalyst; after a final polymerization, adding a chain scission agent to the polymerized polycarbonate to reduce the molecular weight of the polymerized polycarbonate to form a modified polycarbonate having a molecular weight that is less than the molecular weight of the polymerized polycarbonate.
  • a melt polymerization process for adjusting a molecular weight of a polymerized polycarbonate in a melt polymerization process comprises producing the polymerized polycarbonate, wherein the weight average molecular weight of the polymerized polycarbonate based on a polystyrene standard is greater than or equal to 50,000 Daltons (Da) by melt polymerizing a carbonate compound and dihydroxy compound in the presence of a catalyst composition; determining a desired molecular weight; after a final polymerization, adding a chain scission agent to the polymerized polycarbonate to decrease the molecular weight to the desired molecular weight to produce a modified polycarbonate having a branching level that is the same or lower than a branching level of the polymerized polycarbonate.
  • Da 50,000 Daltons
  • a melt polymerization process comprises melt
  • melt polymerization process conditions comprise pressures, temperatures, a residence time, a carbonate compound flow rate, a dihydroxy compound flow rate, and a catalyst flow rate; changing a molecular weight of the polymerized polycarbonate while changing the melt polymerization process conditions by less than 5% to form a modified polycarbonate.
  • a melt polymerization system comprises a carbonate source supply; a dihydroxy compound supply; a catalyst supply; an oligomerization unit in operable communication with the carbonate source supply, the dihydroxy compound supply, and the catalyst supply; a polymerization unit in operable communication with the oligomerization unit; an extruder in operable communication with the polymerization unit; and a chain scission agent supply located downstream of a final polymerization unit and in operable communication with the extruder.
  • FIG. 1 illustrates a process of adding a chain scission agent to a melt polymerization of polycarbonate.
  • the process conditions such as one or more of a monomer flow rate, a catalyst flow rate, a polymerization temperature, a polymerization pressure, and plant throughput are adjusted.
  • the transition time in changing over production to the desired molecular weight polycarbonate can take as many as several hours, resulting in the production of a large amount of waste polycarbonate and/or polycarbonate that does not meet the desired specifications, also referred to herein as off-spec polycarbonate.
  • the Applicants therefore developed a process for producing different molecular weight melt polycarbonates in a production line, without changing the processing conditions.
  • the processing conditions such as pressures, temperatures, carbonate compound flow rate, dihydroxy compound flow rate, and catalyst flow rate
  • the processing conditions can remain the same (i.e., they only fluctuate within normal operating parameters for making a single molecular weight polycarbonate and can specifically vary within 5%, specifically, 1% of a specific value or of a set of values)
  • the process involves producing a higher molecular weight polycarbonate at all times in the polymerization system.
  • the processing conditions are not adjusted to attain a different molecular weight polycarbonate, but remain set to produce a high molecular weight polycarbonate.
  • the molecular weight is reduced to the desired molecular weight (e.g., a final molecular weight) using a chain scission agent that acts to break the polymer chains and modify the molecular weight or the molecular weight is increased to a desired molecular weight by adding a branching agent.
  • a melt polymerization can operate at a set of conditions (for example, of temperature, pressure, residence time, catalyst concentration, monomer flow rate, or a combination comprising one or more of the foregoing, e.g., of temperature, pressure, residence time, and catalyst concentration) that remain within 5%, specifically, 1% of their set values prior to, during, and after the molecular weight adjustment.
  • the melt polymerization process can be operated at conditions such that the polymerized
  • polycarbonate has a melt volume flow rate (MVR) of less than or equal to 7 cubic centimeters per 10 minutes (cm 3 /10 min), specifically, 3 to 7 cm 3 /10 min measured at 300 degrees Celsius (°C) under a load of 1.2 kilograms (kg) according to ASTM D1238-04 prior to the addition of the chain scission agent (i.e., but for the addition of the chain scission agent, the MVR is less than or equal to 7 cm 3 /10 min, specifically, 3 to 7 cm 3 /10 min).
  • the chain scission agent can be added to the polymerized polycarbonate to result in a modified polycarbonate with an
  • the melt polymerization process can be operated at conditions such that the polymerized polycarbonate has a weight average molecular weight (Mw) of greater than 50,000 Daltons, specifically, greater than or equal to 56,000 Daltons, based on a polystyrene standard prior to the addition of the chain scission agent.
  • Mw weight average molecular weight
  • the Mw of the polymerized polycarbonate is greater than 50,000 Daltons, specifically, greater than or equal to 56,000 Daltons.
  • the Mw of the polymerized polycarbonate can be reduced to result in a modified polycarbonate with a weight average molecular weight of less than 50,000 Daltons.
  • polycarbonate can be less than or equal to 500 ppm.
  • the branching level of the polymerized polycarbonate and the modified polycarbonate can be greater than or equal to 500 ppm.
  • the branching level of the modified polycarbonate can be less than or equal to the branching level of the polymerized polycarbonate.
  • the present process can be especially beneficial in a large production facility with a production rate of greater than or equal to 65,000 t/y, specifically, greater than or equal to 100,000 t/y.
  • a standard changeover time to change product MVR from 6 to 65 cm /10 min of 4.5 hours would result in 50 tons of waste and/or off-spec polycarbonate per transition.
  • Reducing the changeover time to 0.5 hour reduces the amount of waste and/or off-spec polycarbonate generated by a factor of ten to only 5 tons of waste polycarbonate per transition and further reducing the changeover time to 0.2 hour reduces the amount of waste generated to only 1.7 tons of waste polycarbonate per transition.
  • significant savings and improvements can be realized with the present process, which is especially evident in large scale melt polycarbonate production plants, e.g., greater than 55,000 t/y, specifically, greater than or equal to 100,000 t/y, more specifically, greater than or equal to 200,000 t/y (91 Mg/day), and even more specifically, greater than or equal to 300,000 t/yr.
  • Polycarbonate as used herein means a polymer having repeating structural carbonate units of formula (1)
  • R 1 groups in which at least 60 percent of the total number of R 1 groups contain aromatic moieties and the balance thereof are aliphatic, alicyclic, or aromatic.
  • Each R 1 can be a C 6 -3o aromatic group, that is, contains at least one aromatic moiety.
  • R 1 can be derived from an aromatic dihydroxy compound of the formula HO-R ⁇ OH, in particular of formula (2)
  • each of A 1 and A2 is a monocyclic divalent aromatic group and Y 1 is a single bond or a bridging group having one or more atoms that separate A 1 from A 2.
  • One atom can separate
  • each R 1 can be derived from a bis henol of formula (3)
  • R a and R b are each independently a halogen, C 1-12 alkoxy, or C 1-12 alkyl; and p and q are each independently integers of 0 to 4. It will be understood that when p or q is less than 4, the valence of each carbon of the ring is filled by hydrogen.
  • X a is a bridging group connecting the two hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each C 6 arylene group are disposed ortho, meta, or para (specifically para) to each other on the C 6 arylene group.
  • the bridging group X a can be a single bond, -0-, -S-, -S(O)-, -S(0) 2 -, -C(O)-, or a C 1-18 organic group.
  • the C 1-18 organic bridging group can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous.
  • the CM S organic group can be disposed such that the C 6 arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the C 1-18 organic bridging group.
  • Each p and q can be 1, and R a and R b can each be a C 1-3 alkyl group, specifically methyl, disposed meta to the hydroxy group on each arylene group.
  • Groups of this type include methylene, cyclohexylmethylene, ethylidene, neopentylidene, and isopropylidene, as well as 2-[2.2.1]-bicycloheptylidene, cyclohexylidene, cyclopentylidene, cyclododecylidene, and adamantylidene.
  • X a can be a C 1-18 alkylene, a C 3-18 cycloalkylene, a fused C 6-18 cycloalkylene, or a group of the formula -B 1 -G-B2 - wherein B 1 and B2 are the same or different Ci_ 6 alkylene and G is a C 3 _i 2 cycloalkylidene or a C 6 -i6 arylene.
  • X a can be a substituted C 3-18 cycloalkylidene of formula 4)
  • R r , R p , R q , and R £ are each independently hydrogen, halogen, oxygen, or C 1-12 hydrocarbon groups;
  • Q is a direct bond, a carbon, or a divalent oxygen, sulfur, or -N(Z)- where Z is hydrogen, halogen, hydroxy, C 1-12 alkyl, C 1-12 alkoxy, or C 1-12 acyl;
  • r is 0 to 2, t is 1 or 2, q is 0 or 1, and k is 0 to 3, with the proviso that at least two of R r , R p , R q , and R £ taken together are a fused cycloaliphatic, aromatic, or heteroaromatic ring.
  • the ring as shown in formula (4) will have an unsaturated carbon-carbon linkage where the ring is fused.
  • the ring as shown in formula (4) contains 4 carbon atoms
  • the ring as shown in formula (4) contains 5 carbon atoms
  • the ring contains 6 carbon atoms.
  • Two adjacent groups e.g., R q and R £ taken together
  • R q and R £ taken together can form one aromatic group
  • R r and R p taken together can form a second aromatic group.
  • R p can be a double- bonded oxygen atom, i.e., a ketone.
  • X a is a cycloalkylidene of formula (4) can be used in the manufacture of polycarbonates containing phthalimidine carbonate units of formula (la)
  • R a , R b , p, and q are as in formula (3), R 3 is each independently a C 1-6 alkyl, j is 0 to 4, and R 4 is hydrogen, Ci_ 6 alkyl, or a substituted or unsubstituted phenyl, for example a phenyl substituted with up to five Ci_ 6 alkyls.
  • the phthalimidine carbonate units are of formula (lb)
  • R 5 is hydrogen, phenyl optionally substituted with up to five 5 C 1-6 alkyls, or C 1-4 alkyl.
  • R 5 can be hydrogen, methyl, or phenyl, specifically phenyl.
  • Carbonate units (lb) wherein R 5 is phenyl can be derived from 2-phenyl-3,3'-bis(4-hydroxy phenyl)phthalimidine (also known as 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-l-one, or N-phenyl phenolphthalein bisphenol (“PPPBP”)).
  • 2-phenyl-3,3'-bis(4-hydroxy phenyl)phthalimidine also known as 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-l-one, or N-phenyl phenolphthalein bisphenol (“PPPBP”)
  • R a and R b are each independently C 1-12 alkyl, p and q are each independently 0 to 4, and R 1 is C 1-12 alkyl, phenyl, optionally substituted with 1 to 5 Ci_io alkyl, or benzyl optionally substituted with 1 to 5 Ci_io alkyl.
  • Each R a and R b can be methyl, p and q can each independently be 0 or 1, and R 1 is C 1-4 alkyl or phenyl.
  • Other examples of bisphenol carbonate units derived from bisphenols (3) wherein X a is a substituted or unsubstituted C 3-18 cycloalkylidene (4) include the
  • R a and R b are each independently C 1-12 alkyl, R g is C 1-12 alkyl, p and q are each independently 0 to 4, and t is 0 to 10. At least one of each of R a and R b can be disposed meta to the cyclohexylidene bridging group.
  • Each R a and R b can independently be Ci_ 4 alkyl, R g is Ci_ 4 alkyl, p and q are each 0 or 1 , and t is 0 to 5.
  • R a , R b , and R g can each be methyl, p and q can each be 0 or 1 , and t can be 0 or 3, specifically 0.
  • Examples of other bisphenol carbonate units derived from bisphenol (3) wherein X a is a substituted or unsubstituted C 3-18 cycloalkylidene include adamantyl units of formula If) and fluorenyl units of formula (lg)
  • At least one of each of R a and R b can be disposed meta to the cycloalkylidene bridging group.
  • R a and R b can each be independently Ci_ 3 alkyl, and p and q can be each 0 or 1 ;
  • R a , R b can each be methyl, p and q are each 0 or 1 , and when p and q are 1 , the methyl group can be disposed meta to the cycloalkylidene bridging group.
  • Carbonates containing units (la) to (lg) are useful for making polycarbonates with high glass transition temperatures (Tg) and high heat distortion temperatures.
  • R h is independently a halogen atom, CM O hydrocarbyl group such as a Ci_io alkyl, a halogen-substituted CM O alkyl, a C 6 io aryl, or a halogen-substituted C 6 io aryl, and n is 0 to 4.
  • the halogen is usually bromine.
  • dihydroxy compounds include the following: 4,4'-dihydroxybiphenyl, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, bis(4- hydroxyphenyl)- 1 -naphthylmethane, 1 ,2-bis(4-hydroxyphenyl)ethane, 1 , 1 -bis(4- hydroxyphenyl)-l-phenylethane, 2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane, bis(4- hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 1,1 -bis
  • bisphenol compounds of formula (3) include l,l-bis(4- hydroxyphenyl) methane, l,l-bis(4-hydroxyphenyl) ethane, 2,2-bis(4-hydroxyphenyl) propane (hereinafter "bisphenol A” or "BPA"), 2,2-bis(4-hydroxyphenyl) butane, 2,2-bis(4- hydroxyphenyl) octane, l,l-bis(4-hydroxyphenyl) propane, l,l-bis(4-hydroxyphenyl) n- butane, 2,2-bis(4-hydroxy-2-methylphenyl) propane, l,l-bis(4-hydroxy-t-butylphenyl) propane, 3,3-bis(4-hydroxyphenyl) phthalimidine, 2-phenyl-3,3-bis(4-hydroxyphenyl) phthalimidine (PPPBPBP
  • the polycarbonate can be a linear homopolymer derived from bisphenol A, in which each of A 1 and A2 is p-phenylene and Y 1 is isopropylidene in formula (3).
  • the polycarbonate is prepared via the melt polymerization of a bisphenol and a carbonate precursor also referred to herein as a carbonate compound.
  • exemplary carbonate precursors include a carbonyl halide such as carbonyl bromide or carbonyl chloride
  • phosgene a bishaloformate of a dihydroxy compound (e.g., the bischloro formate of bisphenol A, hydroquinone ethylene glycol, neopentyl glycol, or the like), diaryl carbonates, or a combination comprising at least one of the foregoing.
  • phosgene a bishaloformate of a dihydroxy compound (e.g., the bischloro formate of bisphenol A, hydroquinone ethylene glycol, neopentyl glycol, or the like), diaryl carbonates, or a combination comprising at least one of the foregoing.
  • the diaryl carbonate ester can be diphenyl carbonate, or an activated diphenyl carbonate having electron-withdrawing substituents on each aryl, such as bis(4-nitrophenyl)carbonate, bis(2-chlorophenyl)carbonate, bis(4-chlorophenyl) carbonate, bis(methyl salicyl)carbonate, bis(4-methylcarboxylphenyl) carbonate, bis(2-acetylphenyl) carboxylate, bis(4-acetylphenyl) carboxylate, or a combination comprising at least one of the foregoing.
  • an activated diphenyl carbonate having electron-withdrawing substituents on each aryl such as bis(4-nitrophenyl)carbonate, bis(2-chlorophenyl)carbonate, bis(4-chlorophenyl) carbonate, bis(methyl salicyl)carbonate, bis(4-methylcarboxylphenyl) carbonate, bis(2-acetylphen
  • branching agents include polyfunctional organic compounds containing at least three functional groups selected from hydroxyl, carboxyl, carboxylic anhydride, haloformyl, and mixtures of the foregoing functional groups.
  • branching agents include aromatic triacyl halides, for example triacyl chlorides of formula 20)
  • Z is a halogen, Ci_ 3 alkyl, Ci_ 3 alkoxy, C 7 _i 2 arylalkylene, C 7 _i 2 alkylarylene, or nitro, and z is 0 to 3; a tri-substituted phenol of formula (21)
  • T is a C 1-2 o alkyl, C 1-2 o alkoxy, C 7-12 arylalkyl, or C 7-12 alkylaryl
  • Y is a halogen, C 1-3 alkyl, C 1-3 alkoxy, C 7-12 arylalkyl, C 7-12 alkylaryl, or nitro
  • s is 0 to 4.
  • branching agents include trimellitic acid, trimellitic anhydride, trimellitic trichloride, tris-p-hydroxyphenylethane, isatin-bis-phenol of formula
  • tris-phenol TC (l,3,5-tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA (4(4(1,1- bis(p-hydroxyphenyl)-ethyl) alpha, alpha-dimethyl benzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid, and benzophenone tetracarboxylic acid.
  • the polycarbonate can be prepared by co- reacting, in a molten state, a dihydroxy reactant and a carbonate precursor in the presence of a transesterification catalyst.
  • the reaction can be carried out in typical polymerization equipment, such as a continuously stirred reactor (CSTR), plug flow reactor, wire wetting fall polymerizers, free fall polymerizers, horizontal polymerizers, wiped film polymerizers, BANBURY mixers, single or twin screw extruders, or a combination comprising one or more of the foregoing.
  • Volatile monohydric phenol is removed from the molten reactants by distillation and the polymer is isolated as a molten residue.
  • Melt polymerization can be conducted as a batch process or as a continuous process. In either case, the melt
  • the polymerization conditions used can comprise two or more distinct reaction stages.
  • the polymerization can comprise a first reaction stage, also referred to as an oligomerization stage, in which the starting dihydroxy aromatic compound and diaryl carbonate are converted into an oligomeric polycarbonate and a second reaction stage, also referred to as a polymerization stage, wherein the oligomeric polycarbonate formed in the first reaction stage is converted to high molecular weight polycarbonate.
  • the oligomerization stage can comprise 1 or more, specifically, 2 or more, more specifically, 2 to 4 oligomerization units (for example 2 to 4 continuously stirred tanks).
  • the polymerization stage can comprise 1 or more, specifically, 2 or more, more specifically, 2 polymerization units (for example 2 horizontal or wire wetting fall polymerizers).
  • the first polymerization unit can polymerize the
  • the polycarbonate composition can then be optionally quenched, and a second polymerization unit can function as a devolitalization unit, where the molecular weight of the polycarbonate does not significantly increase (for example, the molecular weight does not increase by greater than 10 weight percent (wt%)) and a temperature, a pressure, and a residence time are used to reduce the concentration of low molecular weight components (such as those with a molecular weight of less than 1,000 Daltons).
  • wt% weight percent
  • An oligomerization stage polymerization unit is herein defined as a polymerization unit that results in polycarbonate oligomers with a number average molecular weight of less than or equal to 8,000 Daltons and a polymerization stage polymerization unit is herein defined as a polymerization unit that produces polycarbonate with a number average molecular weight of greater than 8,000 Daltons. It is noted that while less than or equal to 8,000 Daltons is used here to define a molecular weight achieved in the first stage, one skilled in the art readily understands that said molecular weight is used to define an oligomerization stage, where the oligomer molecular weight could be greater than 8,000 Daltons.
  • a "staged" polymerization reaction condition can be used in continuous polymerization systems, wherein the starting monomers are oligomerized in a first reaction vessel and the oligomeric polycarbonate formed therein is continuously transferred to one or more downstream reactors in which the oligomeric polycarbonate is converted to high molecular weight polycarbonate.
  • the oligomeric polycarbonate produced has a number average molecular weight of 1,000 to 7,500 Daltons.
  • the number average molecular weight (Mn) of the polycarbonate can be increased to, for example, 8,000 and 25,000 Daltons (using polycarbonate standard), specifically, 13,000 to 18,000 Daltons.
  • reaction temperature can be 100 to 350 °C, specifically, 180 to 310°C.
  • the pressure can be at atmospheric pressure, supra- atmospheric pressure, or a range of pressures from atmospheric pressure to 15 torr in the initial stages of the reaction, and at a reduced pressure at later stages, for example 0.2 to 15 torr.
  • the polymerization can occur in a series of polymerization vessels that can each individually have increasing temperature and/or vacuum.
  • an oligomerization stage can occur at a temperature of 100 to 280°C, specifically, 140 to 240°C and a polymerization stage can occur at a temperature of 240 to 350°C, specifically, 280 to 300°C or 240 to 270°C or 250 to 310°C, where the temperature in the polymerization stage is greater than the temperature in the oligomerization stage.
  • the reaction time from an initial oligomerization unit to a final polymerization unit is generally 0.1 to 15 hours.
  • One or more oligomerization units in the oligomerization stage can each independently be at a pressure of greater than or equal to 100 millibars absolute (mbara).
  • a first oligomerization unit can have a pressure of greater than or equal to 100 mbara and a second oligomerization unit can have a pressure of 15 to 90 mbara, where the first oligomerization unit is upstream of the second oligomerization unit, where one or more first stage oligomerization units can be located before, in between, and/or after said oligomerization units.
  • the polymer can be introduced to a reactor, extruded, subjected to filtration in a melt filter, devolatilized, or a combination comprising one or more of the foregoing. It is noted that the melt filter can be located before or after the extruder.
  • the melt polymerization process for the manufacture of a polycarbonate composition can comprise: melt polymerizing a dihydroxy reactant and a carbonate compound to produce a molten reaction product; quenching the molten reaction product; filtering the molten reaction product in a melt filter upstream of any extruders; optionally, introducing an additive to form a mixture; and extruding the mixture to form the polycarbonate composition.
  • the melt polymerization process for the manufacture of a polycarbonate composition can comprise: melt polymerizing a dihydroxy reactant and a carbonate compound to produce a molten reaction product; introducing a quencher composition and optionally an additive for form a mixture; and extruding the mixture to form the polycarbonate composition.
  • the polymerized polycarbonate can have an endcap level of greater than or equal to 60%, specifically, greater than or equal to 70%, more specifically, greater than or equal to 80%.
  • the endcap level can be determined according to the formula:
  • %EC 100 - (ppm OH + Snell Mn)/340,000 wherein the ppm OH of each sample was measured by FTIR (Perkin Elmer FTIR Spectrum One equipment), dissolving 0.5 grams of the sample in 25 milliliters of dried chloroform. The ppm of OH were calculated measuring the absorbance at 3,584 cm “1 , using a univariable calibration, normalizing the absorbance by diving it by the 2,779 cm "1 absorbance.
  • Catalysts used in the melt transesterification polymerization production of polycarbonates can include alpha (also referred to herein as an alkali catalyst) and/or beta catalysts (also referred to herein as quaternary catalysts). Beta catalysts are typically volatile and degrade at elevated temperatures. Beta catalysts can therefore be used at early low- temperature polymerization stages. Alpha catalysts are typically more thermally stable and less volatile than beta catalysts.
  • the alpha catalyst can comprise a source of alkali and/or alkaline earth ions.
  • the sources of these ions include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, as well as alkaline earth hydroxides such as magnesium hydroxide and calcium hydroxide.
  • alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide
  • alkaline earth hydroxides such as magnesium hydroxide and calcium hydroxide.
  • Other possible sources of alkali and alkaline earth metal ions include the corresponding salts of carboxylic acids (such as sodium acetate) and derivatives of ethylene diamine tetraacetic acid (EDTA) (such as EDTA tetrasodium salt, and EDTA magnesium disodium salt).
  • carboxylic acids such as sodium acetate
  • EDTA ethylene diamine tetraacetic acid
  • alpha transesterification catalysts include alkali or alkaline earth metal salts of carbonate, such as CS 2 CO 3 , NaHC0 3 , and Na 2 C0 3 , and the like, non-volatile inorganic acid such as NaH 2 P0 3 , NaH 2 P0 4 , Na 2 HP0 3 , KH 2 P0 4 , CsH 2 P0 4 , Cs 2 HP0 4 , and the like, or mixed salts of phosphoric acid, such as NaKHP0 4 , CsNaHP0 4 , CsKHP0 4 , and the like. Combinations comprising at least one of any of the foregoing catalysts can be used.
  • the alpha catalyst can be a reduced branching activity or low branching alpha catalyst.
  • a "reduced branching activity alpha catalyst” refers to an alpha catalyst comprising a first alpha catalyst and a second alpha catalyst and/or any reaction product thereof and wherein the reduced alpha catalyst has a reduced branching activity as compared to an alpha catalyst consisting of only the first alpha catalyst.
  • the reduced branching activity alpha catalyst can have a reduced Fries rearrangement activity as compared to an alpha catalyst consisting of only the first alpha catalyst under the same melt polymerization conditions in the melt polymerization of polycarbonate.
  • the alpha catalyst (or first alpha catalyst) can comprise a source of alkali or alkaline earth ions, where the total amount of alkali ions and alkaline earth ions present therein is herein referred to as the "first element," where the first element is the total amount of lithium, sodium, potassium, cesium, rubidium, magnesium, calcium, and strontium present from the first alpha catalyst.
  • Sources of these ions include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, barium hydroxide, strontium hydroxide, and potassium hydroxide, as well as alkaline earth hydroxides such as magnesium hydroxide and calcium hydroxide.
  • alkali and alkaline earth metal ions include the corresponding salts of carboxylic acids (such as sodium acetate, potassium acetate, lithium acetate, calcium acetate, barium acetate, magnesium acetate, and strontium acetate) and derivatives of ethylene diamine tetra acetic acid (EDTA) (such as EDTA tetra sodium salt, and EDTA magnesium disodium salt).
  • carboxylic acids such as sodium acetate, potassium acetate, lithium acetate, calcium acetate, barium acetate, magnesium acetate, and strontium acetate
  • EDTA ethylene diamine tetra acetic acid
  • This alpha catalyst can comprise alkali or alkaline earth metal salts of carbonate, such as CS 2 CO 3 , sodium bicarbonate (NaHC0 3 ), sodium carbonate (Na 2 C0 3 ), potassium bicarbonate, lithium bicarbonate, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, potassium carbonate, lithium carbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, and the like.
  • carbonate such as CS 2 CO 3 , sodium bicarbonate (NaHC0 3 ), sodium carbonate (Na 2 C0 3 ), potassium bicarbonate, lithium bicarbonate, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, potassium carbonate, lithium carbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, and the like.
  • This alpha catalyst can comprise lithium stearate, sodium stearate, strontium stearate, potassium stearate, lithium hydroxyborate, sodium hydroxyborate, sodium phenoxyborate, sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium salts of bisphenol A, dipotassium salts of bisphenol A, and dilithium salts of bisphenol A, sodium salts of phenol, potassium salts of phenol, lithium salts of phenol, or a combination comprising one or more of the foregoing.
  • This alpha catalyst can comprise a combination comprising one or more of the foregoing first alpha catalysts.
  • the second alpha catalyst comprises a non-volatile inorganic acid, where the term "non-volatile” as used herein means that the acid from which the catalyst is made has no appreciable vapor pressure under melt polymerization conditions.
  • non- volatile acids include phosphorous acid, phosphoric acid, sulfuric acid, and metal "oxo acids” such as the oxo acids of germanium, antimony, niobium and the like.
  • Salts of non-volatile acids include alkali metal salts of phosphites; alkaline earth metal salts of phosphites; alkali metal salts of phosphates; alkaline earth metal salts of phosphates; alkali metal salts of sulfates; alkaline earth metal salts of sulfates; alkali metal salts of metal oxo acids; and alkaline earth metal salts of metal oxo acids.
  • salts of non-volatile acids include NaH 2 P0 3 , NaH 2 P0 4 , Na 2 HP0 4 , KH 2 P0 4 , CsH 2 P0 4 , Cs 2 HP0 4 , NaKHP0 4 , NaCsHP0 4 , KCsHP0 4 , Na 2 S0 4 , NaHS0 4 , NaSb0 3 , LiSb0 3 , KSb0 3 , Mg(Sb0 3 ) 2 , Na 2 Ge0 3 , K 2 Ge0 3 , Li 2 Ge0 3 , MgGe0 3 , Mg 2 Ge0 4 , and combinations comprising one or more of the foregoing compounds.
  • the second alpha catalyst comprises a second element, where the second element is equal to the total amount of alkali ions, alkaline earth ions, and metal ions present from the second alpha catalyst, for example, sodium, potassium, cesium, lithium, antimony, magnesium, and germanium.
  • the reduced branching activity alpha catalyst can, for example, comprise a mixture of a first alpha catalyst of NaOH and second alpha catalyst of KH 2 P0 4 . Such a catalyst is referred to herein as KNaHP0 4 .
  • the reduced activity alpha catalyst can have a molar ratio of the first element to the second element (for example, of the Na from NaOH to K from KH 2 P0 4 ) of 0.5 to 1.5, specifically, 0.7 to 1.2.
  • the reduced activity alpha catalyst can be prepared by first dissolving a second alpha catalyst in water to form a first solution.
  • the first solution can comprise, for example, 100 to 4,000, specifically, 1,500 to 2,000 grams of the second alpha catalyst in 20 liters of water.
  • a second solution can be prepared by dissolving a first alpha catalyst in water and allowing the second solution to cool.
  • the second solution can comprise 50 to 3,000, specifically, 800 to 950 grams of the first alpha catalyst 50 wt% solution in 1 liter of water. The second solution is then added to the first solution to form the reduced alpha catalyst solution.
  • the reduced alpha catalyst solution can be titrated to confirm that the reduced alpha catalyst solution comprises 0 to 20,000, specifically, 100 to 10,000 ppm, for example, 6,458 of free second catalyst, for example, free KH 2 P0 4 .
  • the reduced alpha catalyst solution can be combined with additional water, for example, with 500 to 4,000 kg, specifically, 1,000 to 1,500 kg of water in an alpha catalyst tank prior to addition to the polymerization unit.
  • the feed rate of the diluted solution can be 0.1 to 10, specifically, 1 to 5 kilograms per hour (kg/h) into the polymerization unit based on a total monomer feed (i.e.
  • the reactant feed of 10,000 to 20,000 kg/h, specifically, 12,000 to 15,000 kg/h into the polymerization unit and a total bisphenol A feed rate of 5,000 to 9,000 kg/h of dihydroxy monomer to the polymerization unit.
  • the flow rate of the diluted solution can be 0.1 to 10 kg/h, specifically, 1 to 5 kg/h, more specifically, 2 to 3 kg/h into the
  • the diluted solution can be added to a monomer stream to form a catalyst stream and adding the catalyst stream to a polymerization unit. Likewise, a diluted solution can be added to a polymerization at any stage in the
  • polymerization for example, upstream of, and/or directly to, and/or after a monomer mixing unit; and/or upstream of, and/or directly to, and/or after a polymerization unit (for example, to a first stage polymerization unit and/or after the second reaction stage polymerization unit).
  • Possible beta catalysts can comprise a quaternary ammonium compound, a quaternary phosphonium compound, or a combination comprising at least one of the foregoing.
  • the quaternary ammonium compound can be a compound of the structure (R 4 ) 4 N + X ⁇ , wherein each R 4 is the same or different, and is a C 1-2 o alkyl, a C 4 - 2 o cycloalkyl, or a C 4 _2o aryl; and X " is an organic or inorganic anion, for example, a hydroxide, halide, carboxylate, sulfonate, sulfate, formate, carbonate, or bicarbonate.
  • organic quaternary ammonium compounds include tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, tetramethyl ammonium acetate, tetramethyl ammonium formate, tetrabutyl ammonium acetate, and combinations comprising at least one of the foregoing. Tetramethyl ammonium hydroxide is often used.
  • the quaternary phosphonium compound can be a compound of the structure (R 5 ) 4 P + X ⁇ , wherein each R 5 is the same or different, and is a Ci-20 alkyl, a C 4 - 2 o cycloalkyl, or a C 4 _2o aryl; and X " is an organic or inorganic anion, for example, a hydroxide, phenoxide, halide, carboxylate such as acetate or formate, sulfonate, sulfate, formate, carbonate, or bicarbonate.
  • X " is a polyvalent anion such as carbonate or sulfate it is understood that the positive and negative charges in the quaternary ammonium and phosphonium structures are properly balanced.
  • R 20 to R 23 are each methyls and X " is carbonate, it is understood that X - " represents 2(C0 3 - ⁇ 2 ).
  • organic quaternary phosphonium compounds include tetramethyl phosphonium hydroxide, tetramethyl phosphonium acetate, tetramethyl phosphonium formate, tetrabutyl phosphonium hydroxide, tetrabutyl phosphonium acetate (TBPA), tetraphenyl phosphonium acetate (TPPA), tetraphenyl phosphonium phenoxide (TPPP), and combinations comprising at least one of the foregoing.
  • the catalyst can comprise TBPA.
  • the beta catalyst can be a thermo-stabile beta catalyst.
  • the "thermo- stabile beta catalyst” refers to a beta catalyst that is stable for an increased amount of time as compared to a beta catalyst consisting only of TMAOH at the same reaction conditions.
  • the thermo-stabile beta catalyst can be active in the melt polymerization of polycarbonate at a temperature of 150 to 260°C and a pressure of greater than or equal to 100 mbara for an increased time as compared to a beta catalyst consisting of TMAOH at the same reaction conditions.
  • the thermo-stabile beta catalyst can comprise tetraphenyl phosphonium acetate.
  • thermo-stabile beta catalyst can be added to the polymerization unit in a solution of water, for example, in a solution of 10 to 80 wt%, specifically, 30 to 50 wt%, for example, 40 wt% of thermo-stabile beta catalyst in water.
  • the amount of branching in the polycarbonate can affect the impact properties. As a result, too high branching, particularly in lower molecular weight polycarbonates, is undesirable when the polycarbonate will be used in impact required applications. Desirably, when the polycarbonate will be used in impact required applications (such as ophthalmic, electrical meters, cell phone, tablet cases, and the like), the amount of branching in the polycarbonate will be less than or equal to 1,200 ppm, preferably, less than or equal to 900 ppm, and more preferably, less than or equal to 500 ppm.
  • the initial polycarbonate e.g., the higher molecular weight polycarbonate
  • melt polycarbonate produced at lower temperatures and shorter residence times.
  • a higher molecular weight melt polycarbonate often has a branching level of up to 1,600 ppm, e.g., 800 to 1,200 ppm.
  • melt polycarbonate having a weight average molecular weight (measured by gel permeation chromatography (GPC) calibrated on polystyrene standards) (Mw) of 56,000 to 60,000 Daltons, produced using tetrabutyl phosphonium acetate (TBPA) and KNaHP0 4 as the beta and alpha catalysts, will often yield a branching level of 800 to 1,200 ppm.
  • GPC gel permeation chromatography
  • the polycarbonate is to be used as optical quality (OQ) polycarbonate
  • OQ optical quality
  • beta catalyst often used for melt polymerization such as tetramethyl ammonium hydroxide (TMAOH), as well as many other beta catalysts, are thermo-sensitive.
  • TMAOH tetramethyl ammonium hydroxide
  • such catalysts are generally active for only an amount of time in a first oligomerization unit due to their rapid degradation at elevated temperatures, e.g., at temperatures of greater than or equal to 175°C. Therefore, a greater amount of alpha catalyst is needed when producing high Mw melt polycarbonates.
  • the beta catalyst comprises a more thermo- stabile beta catalyst
  • the extent of reaction in the initial stages of the polymerization reaction could be increased allowing for the amount of alpha catalyst added to be reduced.
  • the reduced amount of alpha catalyst present in the process results in a polycarbonate with a reduced Fries rearrangement such that the product polycarbonate can have a branching level of less than 600 ppm, specifically, less than or equal to 500 ppm, more specifically, less than or equal to 450 ppm.
  • a high molecular weight polycarbonate can initially be prepared with a reduced branching level that can be introduced to a chain scission agent to result in a lower molecular weight polycarbonate with good impact properties.
  • the amount of alpha and beta catalyst used can be based upon the total number of moles of dihydroxy compound used in the polymerization reaction.
  • beta catalyst for example, a phosphonium salt
  • the transesterification catalyst can be used in an amount sufficient to provide 1 x 10 - " 8 to 1 x 10 "5 , specifically, 1 x 10 "7 to 8 x 10 "6 , more specifically, 3 x 10 "7 to 2 x 10 "6 moles of catalyst per mole of aromatic dihydroxy compound used.
  • the alpha catalyst can be used in an amount sufficient to provide 1 x 10 - " 2 to 1 x 10 - “ 8 moles, specifically, 1 x 10 - " 4 to 1 x 10 - " 7 moles of metal per mole of the dihydroxy compound used.
  • the amount of beta catalyst (e.g., organic ammonium or phosphonium salts) can be 1 x 10 -2 " to 1 x 10 -5 , specifically 1 x 10 -3 " to 1 x 10 "4 moles per total mole of the dihydroxy compound in the reaction mixture.
  • the amount of alpha catalyst can be less than the amount of beta catalyst added to the polymerization. Quenching of the transesterification catalysts and any reactive catalyst residues with an acidic compound after polymerization is completed can also be useful in some melt polymerization processes. Removal of catalyst residues and/or quenching agent and other volatile residues from the melt polymerization reaction after polymerization can also be useful in some melt polymerization processes.
  • the alpha catalyst can be added to a polymerization at any stage in the polymerization, for example, upstream of, and/or directly to, and/or after a monomer mixing unit; and/or upstream of, and/or directly to, and/or after a polymerization unit (for example, to a first stage polymerization unit and/or the second reaction stage polymerization unit).
  • the catalyst addition process can be free of an alpha catalyst addition step.
  • the beta catalyst can be added to a monomer mixing unit located upstream of a polymerization unit.
  • the process of adding a beta catalyst can comprise adding a beta catalyst and one or both of a dihydroxy monomer and a carbonate source to the monomer mixing unit in any order to form a beta catalyst mixture.
  • the monomer mixing unit can be at atmospheric pressure.
  • the monomer mixing unit can be maintained at a temperature of 100 to 250°C, specifically, 150 to 200°C, more specifically, 165 to 185°C.
  • a quencher composition can be added at one or more locations in the present melt polycarbonate to reduce the activity of the catalyst.
  • the quencher composition comprises a quenching agent (also referred to herein as a quencher).
  • the quenching agent can comprise a sulfonic acid ester such as an alkyl sulfonic ester of the formula R 1 SO 3 R 2 wherein Ri is hydrogen, C 1 -C 12 alkyl, C 6 -Ci 8 aryl, or C 7 -C 1 9 alkylaryl, and R 2 is C 1 -C 12 alkyl, C 6 -Ci 8 aryl, or C 7 -C 1 9 alkylaryl.
  • alkyl sulfonic esters examples include benzenesulfonate, p-toluenesulfonate, methylbenzene sulfonate, ethylbenzene sulfonate, n- butyl benzenesulfonate, octyl benzenesulfonate and phenyl benzenesulfonate, methyl p- toluenesulfonate, ethyl p-toluenesulfonate, n-butyl p-toluene sulfonate, octyl p- toluenesulfonate and phenyl p- toluenesulfonate.
  • the sulfonic acid ester can comprise alkyl tosylates such as n-butyl tosylate.
  • the sulfonic acid ester can be present in the quencher composition in an amount of 0.1 to 10 volume percent (vol%), specifically, 0.1 to 5 vol%, more specifically, 0.5 to 2 vol% based on the total volume of the quencher composition.
  • the quenching agent can comprise boric acid esters (e.g., B(OCH 3 ) 3 ,
  • R is the same as or different from R 15 and has the same definition as R 15 , provided that two of R 15 , R 16 , and R 17 cannot be hydrogen atoms, and m is an integer of 1 to 4, provided that when Y 1 is a single bond, all of X 1 in an amount of m cannot be metal cations of one equivalent, a compound of the formula is a secondary, tertiary or quaternary ammonium cation or a secondary (e.g., tertiary or quaternary phosphonium cation, and Y 1 is a single bond or an oxygen atom, a compound of the formula A 3 -( + X 3 ) n - (R-Y 1 -S0 3 " ) n wherein A 3 is a Ci-C 4 o hydrocarbon group having a valence of n, + X 3 is a secondary, tertiary or quaternary ammonium cation (e.g., NR b 3 +
  • the quencher can be added in an amount of greater than or equal to 5 ppm, specifically, greater than or equal to 10 ppm based on the total amount of the polymerized polycarbonate.
  • the quencher can be added in an amount of less than or equal to 5 ppm, specifically, less than or equal to 10 ppm based on the total amount of the polymerized polycarbonate.
  • the quencher composition can be added to the polymerization unit such that the quencher is added in an amount of 0.5 to 15 ppm, specifically, 1 to 10 ppm, more specifically, 1.5 to 5 ppm, even more specifically, 1.5 to 3 ppm based on the total weight of the polymerized polycarbonate.
  • the quencher composition can be added to the polymerization unit such that the quencher is added in an amount of 5 to 10 ppm, specifically, 6 to 8 ppm based on the total weight of the polymerized polycarbonate.
  • the quencher can be added such that the quencher or derivatives thereof are present in an amount of 0.1 to 50 times, specifically, 0.5 to 30 times, per the neutralization equivalent of the catalyst used.
  • the quencher composition can be added as a liquid or a solid composition at one or more locations in the melt preparation of the polycarbonate.
  • the quencher composition When the quencher composition is added to a polymerization unit and/or to an extruder, the quencher composition can optionally be mixed, for example, by means of a Henschel mixer, and introduced to a feeder, such as a gravimetric feeder, and then fed to a polymerization unit and/or to an extruder through a feeder, such as a side feeder and/or directly into a throat of the extruder.
  • a feeder such as a gravimetric feeder
  • the connecting stream comprising the added quencher composition can be mixed via, for example, the establishment of a turbulent flow, an in-line mixer, for example, a static mixer located in a pipe that contains the connecting stream and/or in a mixer unit that houses a rotating paddle, for example, a continuously stirred tank.
  • an in-line mixer for example, a static mixer located in a pipe that contains the connecting stream and/or in a mixer unit that houses a rotating paddle, for example, a continuously stirred tank.
  • the quencher composition can be added to the connecting stream without mixing.
  • the quencher composition can be added after the formation of the quencher composition
  • polycarbonate composition i.e., after extruding and/or melt filtering.
  • the polycarbonate composition can be mixed with a quencher composition, for example, in an in-line mixer, a twin barrel mixer, or the like, and then pelletized.
  • a quencher composition for example, in an in-line mixer, a twin barrel mixer, or the like
  • polycarbonate composition is prepared, quenched (via the addition of the quencher), the quenched polycarbonate is melt filtered and then devolatilized to remove residual monomers before the addition of additives.
  • the polycarbonate composition can first be pelletized and then the quencher composition can be introduced.
  • the quencher composition can be added, for example, by flowing or spraying, in the solid or liquid form onto polycarbonate pellets and can optionally be mixed with the pellets in, for example, a melt kneader.
  • an additive can be introduced after the introduction of the quencher composition.
  • a pelletized polycarbonate for example, one that is free of an additive, can be combined with a quencher composition and an antioxidant and/or a release agent can then be added.
  • the polycarbonate composition can be devolatized to remove, for example, low Mw polycarbonates (such as those with a molecular weight of less than or equal to 1,000 Daltons).
  • the devolatization can reduce the residual monomer level to an amount of less than 200 ppm based on the total weight of the polymerized polycarbonate and/or can reduce a byproduct level to less than 200 ppm based on the total weight of the polymerized polycarbonate.
  • Devolatization can occur in a polymerization unit (for example, in a second stage polymerization unit), in a reactor, in an extruder, in a mixer, or in a combination comprising one or more of the foregoing.
  • the polycarbonate can be quenched prior to devolatization. For example, a quencher can be added upstream of and/or directly to an extruder, the extruder can be devolatized, and an additive can be added.
  • an amount of water can be added to the extruder to devolatilize the polycarbonate composition.
  • the amount of water that can be introduced can be 0.1 to 10 wt%, specifically, 0.3 to 5 wt% based on the total weight of the polycarbonate composition.
  • the present process has the benefit of being able to easily modify the molecular weight of all or a portion of the polymerized polycarbonate produced without changing the processing parameters, and hence without a several hour changeover process and without large amounts of waste or off- spec polymer.
  • the chain scission agent can be added after a final polymerization (e.g., after a final polymerization unit).
  • "after final polymerization” refers to a time after which the Mw does not increase by greater than 10 wt%. Preferably, the Mw does not increase by greater than or equal to 5 wt% after final polymerization.
  • the chain scission agent can be added upstream of and/or directly to and/or downstream of the devolatization.
  • the chain scission agent can be added upstream of a quencher. It is noted that as used herein, when a first component is added "upstream" of a second component, it is understood that the first component can be added in a location upstream of the addition location of the second component or, where applicable, the first component can be added in the same location, but at a time prior to the addition of the second component.
  • a chain scission agent can be added to a devolatization unit, the polycarbonate can be mixed for an amount of time, and subsequently, a quencher can be added.
  • a chain scission agent can be added to a conduit entering an extruder and a quenching agent can be added directly into the extruder. If a quencher is added upstream of the chain scission agent, then, in addition to the chain scission agent, a catalyst is added, wherein a second quencher can be added downstream of the chain scission agent and catalyst.
  • the chain scission agent can be any agent that breaks the polycarbonate chain, for example, a carbonate source, water, an aryl alcohol, or a combination comprising one or more of the foregoing.
  • the chain scission agent can comprise a diaryl carbonate (such as diphenyl carbonate, di-p-tert-butyl phenol carbonate, di-paracumyl phenol carbonate, di- dicumyl phenol carbonate, bismethyl salicyl carbonate, di-p-hydroxy benzonitrile carbonate), p-hydroxy benzonitrile, paracumyl phenol, p-tert-butyl phenol, dicumyl phenol, methyl phenyl carbonate, dimethyl carbonate, diethyl carbonate, ethyl phenyl carbonate, phenol, a diol (for example, BPA), water, or a combination comprising one or more of the foregoing.
  • a diaryl carbonate such as diphenyl carbonate, di-
  • the chain scission agent can comprise a diaryl carbonate with an electron withdrawing group such as bis(4-nitrophenyl)carbonate, bis(2-chlorophenyl)carbonate, bis(4-chlorophenyl) carbonate, bis(methyl salicyl)carbonate, bis(4-methylcarboxylphenyl) carbonate, bis(2- acetylphenyl) carboxylate, bis(4-acetylphenyl) carboxylate, or a combination comprising one or more of the foregoing.
  • the chain scission agent can comprise a combination comprising at least one of the foregoing chain scission agents.
  • the chain scission agent can comprise a chain scission agent that will not cause a reduction in the endcap level of the resulting polycarbonate, for example, a diaryl carbonate.
  • the chain scission agent can comprise or can consist of diphenyl carbonate (DPC)).
  • DPC diphenyl carbonate
  • the chain scission agent can comprise a monomer used in the polymerization process, water, or an amount of a polymerization by-product. For example, if the polymerization occurring in the
  • polymerization unit is the polymerization of a bisphenol A homopolycarbonate, then the polymerization can occur by the following scheme:
  • diphenyl carbonate reacts with bisphenol A (BPA) to form the polycarbonate (PC) and phenol (PhOH) as a by-product.
  • BPA bisphenol A
  • PhOH phenol
  • Adding one or more of phenol, DPC, or water will act to break the polymer chain to result in a decrease in the molecular weight of the polycarbonate.
  • the chain scission agent can be added as a molten agent (e.g., consisting of the pure molten agent) or can be dissolved in a solvent (for example, anisole, toluene, acetone, or a combination comprising one or more of the foregoing) that is inert to the polymerization.
  • a solvent for example, anisole, toluene, acetone, or a combination comprising one or more of the foregoing
  • the amount of chain scission agent to be added is based upon the molecular weight of the polymerized polycarbonate (e.g., the initial molecular weight), and the desired molecular weight (e.g., final molecular weight).
  • the amount of chain scission agent can be an amount that will reduce the molecular weight of the polymerized polycarbonate to a modified or final molecular weight. The specific amounts can readily be determined.
  • a feedback loop can be employed to monitor the melt polymerization process, where, for example, the viscosity of the polymerized polycarbonate and/or the modified polycarbonate can be monitored and the flow rate of the chain scission agent can be adjusted based on the measured viscosity.
  • the viscosity can be measured, for example, using an inline viscometer or can be determined based on flow and pressure measurements.
  • the initial addition of the carbonate can optionally be the only carbonate addition until after a final polymerization, where a carbonate chain scission agent (e.g., DPC) can be added to reduce the molecular weight to a desired level.
  • a carbonate chain scission agent e.g., DPC
  • no carbonate is introduced after the initial carbonate introduction to the melt polymerization process to react with the dihydroxy compound, until after the final polymerization.
  • FIG. 1 illustrates a melt polycarbonate polymerization system. Initially, dihydroxy reactant A and carbonate compound B are added at a fixed molar ratio along with beta catalyst C to a pre-mix vessel 10 to form a pre-mixture.
  • the pre-mix vessel 10 can be maintained at 160 to 180°C and atmospheric pressure.
  • the pre-mixture, optional additional carbonate compound B, and alpha catalyst D, where the additional carbonate compound B can be the same or different as that added to the pre-mixer, is sent to a first oligomerization vessel 20.
  • the first oligomerization vessel 20 can operate at, for example, a temperature of 230 to 260°C and a vacuum of 140 to 200 millibar atmosphere (mbara).
  • a phenol byproduct from the polymerization reaction in first oligomerization vessel 20 is removed.
  • the mixture then flows into a second oligomerization vessel 21 that can, for example, operate at a higher temperature of 270 to 290°C and a deeper vacuum of 30 to 50 mbara, e.g., for further phenol removal.
  • the prepolymer, as formed in the oligomerization vessel 21, then flows to a first polymerization vessel 30 that can operate, for example, at a temperature of 290 to 315°C and 1 to 2.5 mbara.
  • the effluent from the first polymerization vessel 30 can optionally be split into multiple (e.g., two) second polymerization vessels 31, 32 that can operate, for example, at 290 to 315°C and 0.5 to 1.5 mbara to result in the formation of a molten polycarbonate. It is noted that phenol by-product E and any solvent can be removed, for example, by a scrubber 50, from the oligomerization vessel 20, 21 and/or from the polymerization vessels 30, 31, 32.
  • Chain scission agent F, G can be added to the second polymerization vessels 31, 32, respectively, or downstream thereof, where the chain scission agent F and the chain scission agent G can be the same or different to ultimately result in polycarbonate J, K, respectively, that may or may not have the same molecular weight. It is noted that the process parameters are exemplary and are dependent upon the molecular weight desired.
  • the polycarbonate then flows to an extruder 40, 41 where quencher H, to deactivate polymerization catalyst, and optional additives I are added to the polycarbonate.
  • the extruder 40, 41 can be a twin-screw extruder and at least one of the components can be incorporated into the composition by feeding directly into the extruder 40, 41 at the throat and/or downstream of the throat through, for example, a sidestuffer.
  • Additives I can also be compounded into a masterbatch with a desired polymeric resin and fed into the extruder 40, 41.
  • the extruder 40, 41 can be operated at a temperature higher than allows the composition to flow.
  • the resulting polycarbonate is pumped through a melt filter 60, 61 that can be a stainless steel filter and that has a 2.5 to 50 micrometer, specifically a 10 to 40 micrometer, more specifically a 15 to 30 micrometer mesh size, e.g., to remove gels and other impurities from the polycarbonate J, K.
  • the product can then be stranded in a die-head and finally pelletized and packaged.
  • the pellets, so prepared, when cutting the extrudate can be, for example, one-fourth inch long or less as desired. Such pellets can be used for subsequent molding, shaping, or forming. Typical nominal throughput per line ranges from 3 to 6.6 tons/hour.
  • the present figure illustrates the stream exiting the polymerization vessel 30 as being split into two streams entering polymerization vessels 31, 32, the present process can likewise remain as a single stream or be split into more than two streams.
  • the melt polymerization comprises two or more streams, it is understood that the molecular weight of the produce polycarbonate in each stream independently has a different molecular weight, where at least one of the streams can be prepared without the introduction of a chain scission agent.
  • chain scission agent F, G is illustrated as being added in between the polymerization vessels 31, 32 and the extruder 40, 41, the chain scission agent F, G can likewise be added directly to the extruder 40, 41 (for example, to the throat of the extruder 40, 41 and/or through a side stuff er).
  • the polymerization process can comprise splitting of a polymerized polycarbonate stream into two or more streams that may or may not experience the same polymerization conditions thereafter (i.e., they can attain different molecular weights, have different additives added thereto, etc.).
  • polycarbonate can be prepared in a first portion of the polymerization process; a stream comprising polymerized polycarbonate can be split into two or more streams and directed to 2 or more operating lines.
  • a process can comprise polymerizing polycarbonate in a series of oligomerization units (referred to as the oligomerization stage); a stream exiting the oligomerization stage can be split into two streams (streams A and B), where stream A is directed to polymerization unit A and stream B is directed to polymerization unit B.
  • a process can comprise polymerizing polycarbonate in a series of oligomerization units followed by polymerizing in a series of polymerization units; a stream exiting the polymerization stage can be split into two streams: A and B, where stream A is directed to extruder A and stream B is directed to extruder B.
  • a process can comprise polymerizing polycarbonate in a series of oligomerization units followed by polymerizing in a series of two polymerization units; a stream exiting the first polymerization unit can be split into two streams: A and B, where stream A is directed to second polymerization unit A and stream B is directed to second polymerization unit B.
  • a quencher composition can be added to one or both of streams A and B, where the quencher composition can be the same or different.
  • a chain scission agent can be added to one or more of the streams.
  • An additive can further be added at one or more locations in the present melt preparation of the polycarbonate.
  • the additive can be added upstream of a polymerization unit, directly into a polymerization unit (for example, at an inlet, in a side feeder, in an outlet, or a combination comprising one or more of the foregoing), downstream of a polymerization unit, in a reactor that is not polymerizing polycarbonate, upstream of an extruder, directly into an extruder (for example, at the throat of the extruder, in a side feeder, in an outlet, or a combination comprising one or more of the foregoing), downstream of an extruder, or a combination comprising one or more of the foregoing.
  • the additive can be added as part of the quencher composition and/or can be added separately.
  • quencher composition comprising a heat stabilizer can be added to the polycarbonate and an additive composition comprising a release agent and a UV agent can be added to the quenched composition.
  • the additive can be added in a molten state or can be added after an extruded polycarbonate is re-melted.
  • the additive can be filtered prior to being added into the polymerization unit.
  • the additive can comprise, for example, an impact modifier, a flow modifier, a filler (e.g., a particulate polytetrafluoroethylene (PTFE), glass, carbon, a mineral, or metal), a reinforcing agent (e.g., glass fibers), an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet (UV) agent (such as a UV light stabilizer and a UV absorbing additive), a plasticizer, a lubricant, a release agent (such as a mold release agent (such as glycerol monostearate, pentaerythritol stearate, glycerol tristearate, stearyl stearate, and the like)), an antistatic agent, an antifog agent, an antimicrobial agent, a colorant (e.g, a dye or pigment), a surface effect additive, a radiation stabilizer, a flame retardant, an anti-drip agent (e.g., a PTFE),
  • heat stabilizer additives include organophosphites (e.g.
  • the heat stabilizer can comprise tris(2,4-di-t-butylphenyl) phosphate available as IRGAPHOSTM 168.
  • the heat stabilizer can comprise IRGAPHOSTM 205. Heat stabilizers are generally used in amounts of 0.01 to 5 wt%, based on the total weight of polymer in the composition.
  • antistatic agent refers to monomeric, oligomeric, or polymeric materials that can be processed into polymers and/or sprayed onto materials or articles to improve conductive properties and overall physical performance.
  • monomeric antistatic agents include ethoxylated amines, primary, secondary and tertiary amines, ethoxylated alcohols, alkyl sulfates, alkylarylsulfates, alkylphosphates, alkylaminesulfates, alkyl sulfonate salts such as sodium stearyl sulfonate, sodium dodecylbenzenesulfonate or the like, quaternary ammonium salts, quaternary ammonium polymers, imidazoline derivatives, sorbitan esters, ethanolamides, betaines, or the like, or combinations comprising at least one of the foregoing monomeric antistatic agents.
  • Polymeric antistatic agents include certain polyesteramides, polyether- polyamide (polyetheramide) block copolymers, polyetheresteramide block copolymers, polyetheresters, or polyurethanes, each containing polyalkylene glycol moieties polyalkylene oxide units such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.
  • polyetheramide polyether- polyamide
  • polyetheresteramide block copolymers polyetheresters
  • polyurethanes each containing polyalkylene glycol moieties polyalkylene oxide units such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.
  • Such polymeric antistatic agents are commercially available, for example PELESTATTM 6321 (Sanyo) or PEBAXTM MH1657 (Atofina), IRGASTATTM P18 and P22 (Ciba-Geigy).
  • polymeric materials that can be used as antistatic agents are inherently conducting polymers such as polyaniline (commercially available as PANIPOLTMEB from Panipol), polypyrrole and polythiophene (commercially available from Bayer), which retain some of their intrinsic conductivity after melt processing at elevated temperatures.
  • polyaniline commercially available as PANIPOLTMEB from Panipol
  • polypyrrole commercially available from Bayer
  • polythiophene commercially available from Bayer
  • carbon fibers, carbon nanofibers, carbon nanotubes, carbon black, or a combination comprising at least one of the foregoing can be used in a polymer composition containing chemical antistatic agents to render the composition electrostatically dissipative.
  • Radiation stabilizers can also be present, specifically gamma-radiation stabilizers, gamma-radiation stabilizers include alkylene polyols such as ethylene glycol, propylene glycol, 1,3 -propanediol, 1,2-butanediol, 1,4-butanediol, meso-2,3-butanediol, 1,2- pentanediol, 2,3-pentanediol, 1,4-pentanediol, 1,4-hexandiol, and the like; cycloalkylene polyols such as 1,2-cyclopentanediol, 1,2-cyclohexanediol, and the like; branched
  • alkylenepolyols such as 2,3-dimethyl-2,3-butanediol (pinacol), and the like, as well as alkoxy-substituted cyclic or acyclic alkanes.
  • Unsaturated alkenols are also useful, examples of which include 4-methyl-4-penten-2-ol, 3 -methyl -pentene-3-ol, 2-methyl-4-penten-2-ol, 2,4-dimethyl-4-pene-2-ol, and 9-decen-l-ol, as well as tertiary alcohols that have at least one hydroxy substituted tertiary carbon, for example 2-methyl-2,4-pentanediol (hexylene glycol), 2-phenyl-2-butanol, 3-hydroxy-3-methyl-2-butanone, 2-phenyl-2-butanol, and the like, and cyclic tertiary alcohols such as 1 -hydroxy- 1-methyl-cyclohe
  • hydroxymethyl aromatic compounds that have hydroxy substitution on a saturated carbon attached to an unsaturated carbon in an aromatic ring can also be used.
  • the hydroxy-substituted saturated carbon can be a methylol group (-CH 2 OH) or it can be a member of a more complex hydrocarbon group such as -CR 4 HOH or -CR 2 4 OH wherein R 4 is a complex or a simple hydrocarbon.
  • Specific hydroxy methyl aromatic compounds include benzhydrol, 1,3- benzenedimethanol, benzyl alcohol, 4-benzyloxy benzyl alcohol and benzyl benzyl alcohol.
  • 2-Methyl-2,4-pentanediol, polyethylene glycol, and polypropylene glycol are often used for gamma-radiation stabilization.
  • Colorants such as pigment and/or dye additives can also be present.
  • Useful pigments can include, for example, inorganic pigments such as metal oxides and mixed metal oxides such as zinc oxide, titanium dioxides, iron oxides, or the like; sulfides such as zinc sulfides, or the like; aluminates; sodium sulfo- silicates sulfates, chromates, or the like; carbon blacks; zinc ferrites; ultramarine blue; organic pigments such as azos, di-azos, quinacridones, perylenes, naphthalene tetracarboxylic acids, flavanthrones, isoindolinones,
  • Pigment Red 101 Pigment Red 122, Pigment Red 149, Pigment Red 177, Pigment Red 179, Pigment Red 202, Pigment Violet 29, Pigment Blue 15, Pigment Blue 60, Pigment Green 7, Pigment Yellow 119, Pigment Yellow 147, Pigment Yellow 150, and Pigment Brown 24; or combinations comprising at least one of the foregoing pigments.
  • Dyes are generally organic materials and include coumarin dyes such as coumarin 460 (blue), coumarin 6 (green), nile red or the like; lanthanide complexes;
  • hydrocarbon and substituted hydrocarbon dyes polycyclic aromatic hydrocarbon dyes
  • scintillation dyes such as oxazole or oxadiazole dyes; aryl- or heteroaryl-substituted poly (C 2 _ s) olefin dyes; carbocyanine dyes; indanthrone dyes; phthalocyanine dyes; oxazine dyes; carbostyryl dyes; napthalenetetracarboxylic acid dyes; porphyrin dyes; bis(styryl)biphenyl dyes; acridine dyes; anthraquinone dyes; cyanine dyes; methine dyes; arylmethane dyes; azo dyes; indigoid dyes, thioindigoid dyes, diazonium dyes; nitro dyes; quinone imine dyes; aminoketone dyes; tetrazolium dyes; thiazole dyes; perylene dyes, perinone dyes; bis- benzoxazolyl
  • phenoxazonium perchlorate 2-(l-naphthyl)-5-phenyloxazole; 2,2'-p-phenylen-bis(5-phenyl oxazole); rhodamine 700; rhodamine 800; pyrene, chrysene, rubrene, coronene, or the like; or combinations comprising at least one of the foregoing dyes.
  • Possible fillers or reinforcing agents include, for example, mica, clay, feldspar, quartz, quartzite, perlite, tripoli, diatomaceous earth, aluminum silicate (mullite), synthetic calcium silicate, fused silica, fumed silica, sand, boron-nitride powder, boron-silicate powder, calcium sulfate, calcium carbonates (such as chalk, limestone, marble, and synthetic precipitated calcium carbonates) talc (including fibrous, modular, needle shaped, and lamellar talc), wollastonite, hollow or solid glass spheres, silicate spheres, cenospheres, alumino silicate or armospheres, kaolin, whiskers of silicon carbide, alumina, boron carbide, iron, nickel, or copper, continuous and chopped carbon fibers or glass fibers, molybdenum sulfide, zinc sulfide, barium titanate, barium ferrite, barium sulf
  • the fillers and reinforcing agents can be coated with a layer of metallic material to facilitate conductivity, or surface treated with silanes to improve adhesion and dispersion with the polymer matrix.
  • Fillers are used in amounts of 1 to 200 parts by weight, based on 100 parts by weight of based on 100 parts by weight of the total composition.
  • Antioxidant additives include organophosphites such as tris(nonyl)
  • phenyl)phosphite tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-butylphenyl)
  • pentaerythritol diphosphite distearyl pentaerythritol diphosphite; alkylated monophenols or polyphenols; alkylated reaction products of polyphenols with dienes, such as tetrakis
  • UV absorbing additives include hydroxybenzophenones; hydroxy
  • benzotriazoles hydroxybenzotriazines; cyanoacrylates; oxanilides; benzoxazinones; aryl salicylates; monoesters of diphenols such as resorcinol monobenzoate; 2-(2H-benzotriazol-2- yl)-4-(l,l,3,3-tetramethylbutyl)-phenol (CYASORBTM 5411); 2-hydroxy-4-n-octyloxy benzophenone (CYASORBTM 531); 2-[4,6-bis(2,4-dimethylphenyl)-l,3,5-triazin-2-yl]- 5- (octyloxy)-phenol (CYASORBTM 1164); 2,2'-(l,4- phenylene)bis(4H-3,l-benzoxazin-4-one) (CYASORBTM UV- 3638); poly[(6-morphilino-s-triazine-2,4-diyl)[2,
  • UV absorbers can be used in amounts of 0.01 to 1 part by weight, based on 100 parts by weight of polycarbonate and impact modifier.
  • UV absorbers that can be particularly useful with the polycarbonate compositions disclosed herein include 2-(2H-benzotriazol-2- yl)-4-(l,l,3,3-tetramethylbutyl)-phenol (e.g., CYASORBTM 5411 commercially available from Cytec Industries, Inc., Woodland Park, New Jersey) and 2,2'-(l,4- phenylene)bis(4H- 3,l-benzoxazin-4-one) (e.g., CYASORBTM UV- 3638, commercially available from Cytec Industries, Inc., Woodland Park, New Jersey), and combinations comprising at least one of the foregoing.
  • the UV stabilizers can be present in an amount of 0.01 to 1 wt%, specifically, 0.1 to 0.5 wt%, and more specifically, 0.15 to 0.4 wt%, based upon the total weight of the
  • Plasticizers, lubricants, and/or mold release agents can also be used.
  • materials which include, for example, phthalic acid esters such as dioctyl-4,5-epoxy-hexahydrophthalate; tris-(octoxycarbonylethyl) isocyanurate; tristearin; di- or polyfunctional aromatic phosphates such as resorcinol tetraphenyl diphosphate (RDP), the bis(diphenyl) phosphate of hydroquinone and the bis(diphenyl) phosphate of bisphenol A; poly-alpha-olefins; epoxidized soybean oil;
  • phthalic acid esters such as dioctyl-4,5-epoxy-hexahydrophthalate
  • tris-(octoxycarbonylethyl) isocyanurate tristearin
  • di- or polyfunctional aromatic phosphates such as resorcinol tetraphenyl diphosphate (R
  • silicones including silicone oils
  • esters for example, fatty acid esters such as alkyl stearyl esters, e.g., methyl stearate, stearyl stearate, pentaerythritol tetrastearate, and the like;
  • combinations of methyl stearate and hydrophilic and hydrophobic nonionic surfactants comprising polyethylene glycol polymers, polypropylene glycol polymers, poly(ethylene glycol-co-propylene glycol) copolymers, or a combination comprising at least one of the foregoing glycol polymers, e.g., methyl stearate and polyethylene-polypropylene glycol copolymer in a suitable solvent; waxes such as beeswax, montan wax, paraffin wax, or the like.
  • the plasticizers, lubricants, and/or mold release agent can comprise compound of formula (I)
  • Ri, R 2 , and R 3 can be the same or different hydrocarbon chains with 8 to 20 carbon atoms and 0 to 6 unsaturations, wherein Ri, R 2 , and R 3 are each independently selected from C 8 -C 2 o alkyl, C 8 -C 2 o haloalkyl, C 8 -C 2 o polyhaloalkyl, C 8 -C 2 o alkene, and C 8 -C 2 o alkoxy. Ri, R 2 , and R 3 can each independently be from Ci 7 H 3 5 or all Ri, R 2 , and R 3 can be Ci 7 H 3 5.
  • the plasticizers, lubricants, and/or mold release agent can comprise glycerol monostearate, glycerol monopalmitate, glycerol tristearate, glycerol tristearate, stearyl stearate, or a combination comprising one or more of the foregoing.
  • One or more of the aforementioned can have an acid value of 2 to 20 milligrams (mg) KOH as determined by: adding 100 milliliters (ml) of isopropanol to 2.5 grams (g) of a partial ester to thereby dissolve the partial ester; phenolphthalein is added to the resultant solution as an indicator; titrating the resultant mixture using a 0.1 moles per liter (mol/L) standard solution of potassium hydroxide to thereby obtain the acid value (mg KOH).
  • the amount of the partial ester subjected to measurement is changed to 20 g; when it is expected that the partial ester has an acid value of from 1 to 4, the amount of the partial ester subjected to measurement is changed to 10 g; and when it is expected that the partial ester has an acid value of 15 or more, the amount of the partial ester subjected to measurement is changed to 0.5 g.
  • the plasticizers, lubricants, and/or mold release agent can be present in an amount of 0.01 to 5 parts by weight, specifically, 0.01 to 0.1 parts by weight, based on 100 parts by weight of polycarbonate and impact modifier.
  • Useful flame retardants include organic compounds that include phosphorus, bromine, and/or chlorine.
  • Non-brominated and non-chlorinated phosphorus -containing flame retardants can be preferred in certain applications for regulatory reasons, for example organic phosphates and organic compounds containing phosphorus -nitrogen bonds.
  • Flame retardant aromatic phosphates include triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate, phenyl bis(dodecyl) phosphate, phenyl bis(neopentyl) phosphate, phenyl bis(3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl) p-tolyl phosphate, tritolyl phosphate, bis(2-ethylhexyl) phenyl phosphate, tri(nonylphenyl) phosphate, bis(dodecyl) p- tolyl phosphate, dibutyl phenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl bis(2,
  • Di- or polyfunctional aromatic phosphorus -containing compounds are also useful, for example resorcinol tetraphenyl diphosphate (RDP), the bis(diphenyl) phosphate of hydroquinone and the bis(diphenyl) phosphate of bisphenol A, respectively, and their oligomeric and polymeric counterparts.
  • Flame retardant compounds containing phosphorus-nitrogen bonds include phosphonitrilic chloride, phosphorus ester amides, phosphoric acid amides, phosphonic acid amides, phosphinic acid amides, and tris(aziridinyl) phosphine oxide.
  • phosphorus-containing flame retardants are present in amounts of 0.1 to 30 parts by weight, more specifically 1 to 20 parts by weight, based on 100 parts by weight of the total composition, excluding any filler.
  • Halogenated materials can also be used as flame retardants, for example bisphenols of which the following are representative: 2,2-bis-(3,5-dichlorophenyl)-propane; bis-(2-chlorophenyl)-methane; bis(2,6-dibromophenyl)-methane; l,l-bis-(4-iodophenyl)- ethane; l,2-bis-(2,6-dichlorophenyl)-ethane; l,l-bis-(2-chloro-4-iodophenyl)ethane; 1,1-bis- (2-chloro-4-methylphenyl)-ethane; l,l-bis-(3,5-dichlorophenyl)-ethane; 2,2-bis-(3-phenyl-4- bromophenyl) -ethane; 2,6-bis-(4,6-dichloronaphthyl)-propane; and
  • halogenated materials include 1,3-dichlorobenzene, 1,4-dibromobenzene, l,3-dichloro-4-hydroxybenzene, and biphenyls such as 2,2'-dichlorobiphenyl, polybrominated 1,4-diphenoxybenzene, 2,4'- dibromobiphenyl, and 2,4'-dichlorobiphenyl as well as decabromo diphenyl oxide, as well as oligomeric and polymeric halogenated aromatic compounds, such as a copolycarbonate of bisphenol A and tetrabromobisphenol A and a carbonate precursor, e.g., phosgene.
  • biphenyls such as 2,2'-dichlorobiphenyl, polybrominated 1,4-diphenoxybenzene, 2,4'- dibromobiphenyl, and 2,4'-dichlorobiphenyl as well as decabromo diphenyl oxide, as well as oligo
  • Metal synergists e.g., antimony oxide
  • halogen containing flame retardants are present in amounts of 1 to 25 parts by weight, more specifically 2 to 20 parts by weight, based on 100 parts by weight of the total composition, excluding any filler.
  • Inorganic flame retardants can also be used, for example salts of C 1-16 alkyl sulfonate salts such as potassium perfluorobutane sulfonate (Rimar salt), potassium perfluoroctane sulfonate, tetraethylammonium perfluorohexane sulfonate, and potassium diphenylsulfone sulfonate; salts such as Na 2 C0 3 , K 2 C0 3 , MgC0 3 , CaC0 3 , and BaC0 3 , or fluoro-anion complexes such as Li 3 AlF 6 , BaSiF 6 , KBF 4 , K 3 A1F 6 , KA1F 4 , K 2 SiF 6 , and/or Na 3 AlF 6 .
  • inorganic flame retardant salts are present in amounts of 0.01 to 10 parts by weight, more specifically 0.02 to 1 parts by weight, based on 100 parts by
  • Anti-drip agents can also be used in the composition, for example a fibril forming or non-fibril forming fluoropolymer such as polytetrafluoroethylene (PTFE).
  • the anti-drip agent can be encapsulated by a rigid copolymer, for example styrene-acrylonitrile copolymer (SAN).
  • SAN styrene-acrylonitrile copolymer
  • TSAN styrene-acrylonitrile copolymer
  • a TSAN comprises 50 wt% PTFE and 50 wt% SAN, based on the total weight of the encapsulated fluoropolymer.
  • the SAN can comprise, for example, 75 wt% styrene and 25 wt% acrylonitrile based on the total weight of the copolymer.
  • Antidrip agents can be used in amounts of 0.1 to 10 parts by weight, based on 100 parts by weight of the total composition, excluding any filler.
  • the quenched composition can be essentially free of chlorine and bromine.
  • Essentially free of chlorine and bromine is defined as having a bromine and/or chlorine content of less than or equal to 100 ppm, less than or equal to 75 ppm, or less than or equal to 50 ppm, based on the total parts by weight of the composition, excluding any filler.
  • the quenched composition can have a light transparency of greater than 90% as determined using 3.2 mm thick samples using ASTM D 1003-00, Procedure B using CIE standard illuminant C, with unidirectional viewing. Accordingly, when the quenched composition has such a light transparency, it is herein referred to as an "optical grade" composition.
  • the molecular weight was measured by GPC using
  • %EC 100 - (ppm OH + Snell Mn)/340,000 wherein the ppm OH of each sample was measured by FTIR (Perkin Elmer FTIR Spectrum One equipment), dissolving 0.5 grams of the sample in 25 milliliters of dried chloroform. The ppm of OH were calculated measuring the absorbance at 3,584 cm “1 , using a univariable calibration, normalizing the absorbance by diving it by the 2,779 cm "1 absorbance.
  • the outlet stream of the first oligomerization unit was then pumped to a stirred second oligomerization unit that was operated at 280°C and 37 mbar vacuum.
  • the outlet stream of the second oligomerization unit was pumped to the polymerization section where two horizontal reactors (polymerizers) in series are used to reach the final viscosity target.
  • the first polymerizer operated at 300 °C and 2.5 to 3.0 mbar vacuum and the second polymerizer operated at 1.0 to 1.5 mbar vacuum and 302°C.
  • the polymer stream from the second polymerizer was sent to a downstream 6 barrel twin screw finishing extruder (length to diameter ratio of 21, and a diameter of 44 millimeters). The barrel temperature was set at 300°C and screw ran at 100 revolutions per minute.
  • Examples 2-4 a diphenyl carbonate stream was added in the outlet of the second polymerizer.
  • the diphenyl carbonate was mixed with the polycarbonate using an in- line static mixer located in the feeding pipe to the extruder.
  • the molecular weight and the endcap levels were determined for Examples 1-4 and are shown in Table 1.
  • Table 1 shows that adding an amount of DPC to the polycarbonate results in a decrease in molecular weight and an increase in the endcap level.
  • a single melt polycarbonate production line can be used to produce multiple different Mw
  • the multiple different Mw polycarbonates can, if desired, be produced without a reduction in the endcapping level of the polycarbonate. Therefore, the addition of chain scission agent (e.g., a diaryl carbonate, methyl phenyl carbonate, dimethyl carbonate, diethyl carbonate, ethyl phenyl carbonate, phenol, or a combination comprising one or more of the foregoing) to the polymerized polycarbonate can be employed to enable a plant to efficiently produce multiple Mw polycarbonates, and can produce them without a reduction (or with an increase) in endcapping level.
  • the increase in endcapping level can be greater than or equal to 3%, specifically, greater than or equal to 5%, and even greater than or equal to 10%, as compared to the polycarbonate before the Mw reduction.
  • a melt polycarbonate with an MVR of 6.0 cm 3 / 10 min as determined at 300°C under a load of 1.2 kg according to ASTM D1238-04 was run through an extruder and a chain scission agent was added.
  • Table 2 shows Examples 5-11, where either phenol (P) or water (W) was added to the inlet (I) or to barrel 4 (B) of the extruder and the MVR and endcap were determined.
  • MVR (cm 3 /10 min) 28 62 32 45 12 40 16 >200 23 [0100]
  • Table 2 shows that adding water or phenol to a melt polycarbonate results in an increase in MVR. This increase in MVR corresponds to a decrease in molecular weight. Table 2 further shows that adding phenol or water resulted in a decrease in the endcap level.
  • Embodiment 1 a melt polymerization process comprises melt polymerizing a carbonate compound and dihydroxy compound in the presence of a catalyst composition to form a polymerized polycarbonate, wherein the catalyst composition comprises an alpha catalyst and/or a beta catalyst; after a final polymerization, adding a chain scission agent to the polymerized polycarbonate to reduce a molecular weight of the polymerized
  • Embodiment 2 a melt polymerization process for adjusting a molecular weight of a polymerized polycarbonate in a melt polymerization process comprises producing the polymerized polycarbonate, wherein the weight average molecular weight of the polymerized polycarbonate based on a polystyrene standard is greater than or equal to 50,000 Daltons by melt polymerizing a carbonate compound and dihydroxy compound in the presence of a catalyst composition; determining a desired molecular weight; after a final polymerization, adding a chain scission agent to the polymerized polycarbonate to decrease the molecular weight to the desired molecular weight to produce a modified polycarbonate having a branching level that is the same or lower than a branching level of the polymerized polycarbonate.
  • Embodiment 3 the process of Embodiment 2, further comprising monitoring the molecular weight of the modified polycarbonate with a controller and wherein the controller automatically adds an amount of the chain scission agent based upon a monitored modified polycarbonate molecular weight and the desired molecular weight.
  • Embodiment 4 the process of any of Embodiments 2-3, wherein the desired molecular weight is based upon an intended use of the modified polycarbonate.
  • Embodiment 5 a melt polymerization process comprising melt polymerizing a carbonate compound and dihydroxy compound in the presence of a catalyst composition under melt polymerization process conditions to form a polymerized polycarbonate, wherein the melt polymerization process conditions comprise pressures, temperatures, a residence time, a carbonate compound flow rate, a dihydroxy compound flow rate, and a catalyst flow rate; changing a molecular weight of the polymerized polycarbonate while changing the melt polymerization process conditions by less than 5% to form a modified polycarbonate.
  • Embodiment 6 the process of Embodiment 5, comprising changing the melt polymerization process conditions by less than or equal to 3%.
  • Embodiment 7 the process of Embodiment 6, comprising changing the melt polymerization process conditions by less than or equal to 1%.
  • Embodiment 8 the process of any of Embodiments 5-7, wherein the changing of the molecular weight comprises adding a branching agent to the polymerized
  • Embodiment 9 the process of Embodiment 8, wherein the branching agent comprises trimellitic acid, trimellitic anhydride, trimellitic trichloride, tris-p-hydroxy phenylethane, isatin-bis-phenol of formula (22), tris-phenol TC (l,3,5-tris((p-hydroxy phenyl)isopropyl)benzene), tris-phenol PA (4(4(1, l-bis(p-hydroxyphenyl)-ethyl) alpha, alpha-dimethyl benzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid, benzo phenone tetracarboxylic acid, or a combination comprising one or more of the foregoing.
  • the branching agent comprises trimellitic acid, trimellitic anhydride, trimellitic trichloride, tris-p-hydroxy phenylethane, isatin-bis-phenol of formula (22), tris-phenol TC (
  • Embodiment 10 the process of any of Embodiments 5-7, wherein the changing of the molecular weight comprises adding a chain scission agent to the polymerized polycarbonate.
  • Embodiment 11 the process of any of Embodiments 1-5 and 10, wherein the chain scission agent comprises a carbonate source, water, an aryl alcohol, or a combination comprising one or more of the foregoing.
  • Embodiment 12 the process of any of Embodiments 1-5 and 10-11, wherein the chain scission agent comprises a diaryl carbonate, p-hydroxy benzonitrile, paracumyl phenol, p-tert-butyl phenol, dicumyl phenol, methyl phenyl carbonate, dimethyl carbonate, diethyl carbonate, ethyl phenyl carbonate, phenol, or a combination comprising one or more of the foregoing.
  • the chain scission agent comprises a diaryl carbonate, p-hydroxy benzonitrile, paracumyl phenol, p-tert-butyl phenol, dicumyl phenol, methyl phenyl carbonate, dimethyl carbonate, diethyl carbonate, ethyl phenyl carbonate, phenol, or a combination comprising one or more of the foregoing.
  • Embodiment 13 the process of any of Embodiments 1-5 and 10-12, wherein the chain scission agent comprises diphenyl carbonate, di-p-tert-butyl phenol carbonate, di- paracumyl phenol carbonate, di-dicumyl phenol carbonate, bismethyl salicyl carbonate, di-p- hydroxy benzonitrile carbonate, or a combination comprising at least one of the foregoing, specifically, the chain scission agent comprises diphenyl carbonate.
  • Embodiment 14 the process of any of Embodiments 1-5 and 10-13, further comprising adding a quenching agent to the modified polycarbonate after adding the chain scission agent.
  • Embodiment 15 the process of any of Embodiments 1-14, further comprising splitting the polymerized polycarbonate into greater than or equal to two streams; and wherein the chain scission agent is added to at least one of the streams.
  • Embodiment 16 the process of Embodiment 15, wherein a second modified polycarbonate is produced having a different molecular weight than the modified
  • Embodiment 17 the process of any of Embodiments 1-16, wherein the modified polycarbonate is an optical grade polycarbonate having a light transparency of greater than 90% as determined using 3.2 mm thick samples using ASTM D 1003-00, Procedure B using CIE standard illuminant C, with unidirectional viewing.
  • the modified polycarbonate is an optical grade polycarbonate having a light transparency of greater than 90% as determined using 3.2 mm thick samples using ASTM D 1003-00, Procedure B using CIE standard illuminant C, with unidirectional viewing.
  • Embodiment 18 the process of any of Embodiments 1-17, wherein the polymerized polycarbonate has a molecular weight of greater than 50,000 Daltons.
  • Embodiment 19 the process of any of Embodiments 1-18, wherein the polymerized polycarbonate has a molecular weight of greater than or equal to 56,000 Daltons.
  • Embodiment 20 the process of any of Embodiments 1-19, wherein the modified polycarbonate has a molecular weight of less than or equal to 45,000 Daltons.
  • Embodiment 21 the process of any of Embodiments 1-20, wherein the modified polycarbonate has a molecular weight of less than or equal to 45,000 Daltons.
  • Embodiment 22 the process of any of Embodiments 1-21, wherein the catalyst comprises a beta catalyst and the beta catalyst comprises tetraphenyl phosphonium acetate, tetraphenyl phosphonium phenoxide, or a combination comprising one or both of the foregoing.
  • Embodiment 23 the process of any of Embodiments 1-22, wherein prior to the final polymerization, carbonate is introduced only once.
  • Embodiment 24 the process of any of Embodiments 1-23, wherein the modified polycarbonate has a branching level of less than or equal to 500 ppm.
  • Embodiment 25 the process of any of Embodiments 1-24, wherein the modified polycarbonate has a branching level of less than or equal to 400 ppm.
  • Embodiment 26 the process of any of Embodiments 1-25, wherein the polymerized polycarbonate has an endcap level of greater than or equal to 60%.
  • Embodiment 27 the process of Embodiment 26, wherein the end cap level is greater than or equal to 70% or greater than or equal to 75%.
  • Embodiment 28 the process of Embodiment 27, wherein the end cap level is greater than or equal to 80%.
  • Embodiment 29 the process of any of Embodiments 1-28, wherein the catalyst comprises a beta catalyst and the beta catalyst comprises tetraphenyl phosphonium acetate.
  • Embodiment 30 the process of any of Embodiments 1-29, further comprising adding a quencher composition after the addition of the chain scission agent, wherein the adding comprises mixing the quencher composition with the polymerized polycarbonate for a period of time of greater than or equal to 5 seconds prior to the addition to the polycarbonate of any reactive additive, wherein the reactive additive has a reactive OH group or reactive ester group.
  • Embodiment 31 the process of Embodiment 30, wherein the quencher composition comprises 1 to 10 ppm alkyl tosylate and/or 1 to 10 ppm phosphorous acid, based upon 100 parts of the modified polycarbonate.
  • Embodiment 32 the process of any of Embodiments 30-31, wherein the quencher composition is added at a pressure of greater than or equal to 2 bars.
  • Embodiment 33 the process of any of the preceding Embodiments, wherein the modified polycarbonate has an increase in endcapping level of greater than or equal to 3%, or greater than or equal to 5%, or greater than or equal to 10%, as compared to an endcapping level of the polymerized polycarbonate.
  • Embodiment 34 a melt polymerization system, comprising a carbonate source supply; a dihydroxy compound supply; a catalyst supply; an oligomerization unit in operable communication with the carbonate source supply, the dihydroxy compound supply, and the catalyst supply; a polymerization unit in operable communication with the oligomerization unit; an extruder in operable communication with the polymerization unit; and a chain scission agent supply located downstream of a final polymerization unit and in operable communication with the extruder.
  • Embodiment 35 the system of Embodiment 34, further comprising a premix vessel configured to mix a carbonate from the carbonate source, a dihydroxy compound from the dihydroxy compound source, and a catalyst from the catalyst source, wherein the premix vessel is upstream from and in operable communication with the oligomerization unit.
  • Embodiment 36 the system of any of Embodiments 34-35, further comprising a carbonate compound inlet upstream of and/or into the oligomerization unit and downstream of the premix vessel.
  • Embodiment 37 the system of any of Embodiments 34-36, further comprising a quencher inlet for adding a quencher such that the quencher composition can be mixed with the polymerized polycarbonate for a period an alpha catalyst supply configured to introduce an alpha catalyst upstream of time of greater than and/or equal to 5 seconds prior to the addition to the polycarbonate of any reactive additive, wherein the reactive.
  • Embodiment 38 the system of any of Embodiments 34-37, further comprising a quencher inlet for adding a quencher such that the quencher composition can be mixed with the polymerized polycarbonate for a period of time of greater than or equal to 5 seconds prior to the addition to the polycarbonate of any reactive additive, wherein the reactive additive has a reactive OH group or reactive ester group.
  • Embodiment 39 the system of Embodiment 38, wherein the quencher composition comprises 1 to 10 ppm of a sulfonic acid ester, based upon 100 parts of the polymerized polycarbonate; and/or 1 to 10 ppm phosphorous acid, based upon 100 parts of the polymerized polycarbonate.
  • Embodiment 40 the process of any of Embodiments 1-5 and 10-33, wherein the chain scission agent comprises bis(4-nitrophenyl)carbonate, bis(2- chlorophenyl)carbonate, bis(4-chlorophenyl) carbonate, bis(methyl salicyl)carbonate, bis(4- methylcarboxylphenyl) carbonate, bis(2-acetylphenyl) carboxylate, bis(4-acetylphenyl) carboxylate, diphenyl carbonate, di-p-tert-butyl phenol carbonate, di-paracumyl phenol carbonate, di-dicumyl phenol carbonate, bismethyl salicyl carbonate, di-p-hydroxy benzonitrile carbonate), p-hydroxy benzonitrile, paracumyl phenol, p-tert-butyl phenol, dicumyl phenol, methyl phenyl carbonate, dimethyl carbonate, diethyl carbonate, eth
  • the invention may alternately comprise, consist of, or consist essentially of, any appropriate components herein disclosed.
  • the invention may additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any components, materials, ingredients, adjuvants or species used in the prior art compositions or that are otherwise not necessary to the achievement of the function and/or objectives of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

Dans un mode de réalisation, l'invention concerne un procédé de polymérisation en masse fondue comprenant la polymérisation en masse fondue d'un composé carbonate et d'un composé dihydroxy en présence d'une composition catalytique pour former un polycarbonate polymérisé, la composition catalytique comprenant un catalyseur de métal alcalin et/ou un catalyseur quaternaire ; après une polymérisation finale, l'addition d'un agent de scission de chaîne au polycarbonate polymérisé afin de réduire le poids moléculaire du polycarbonate polymérisé pour former un polycarbonate modifié présentant un poids moléculaire qui est inférieur au poids moléculaire du polycarbonate polymérisé.
PCT/IB2015/052605 2014-04-11 2015-04-09 Système et procédé destinés à la production de polycarbonates de divers poids moléculaires à en masse fondue WO2015155737A1 (fr)

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US15/111,271 US20170015784A1 (en) 2014-04-11 2015-04-09 A system and process for producing various molecular weight melt polycarbonates
CN201580012057.6A CN106068295B (zh) 2014-04-11 2015-04-09 用于生产多种分子量熔融聚碳酸酯的系统和方法
KR1020167029663A KR102165343B1 (ko) 2014-04-11 2015-04-09 다양한 분자량의 용융 폴리카보네이트를 제조하는 시스템 및 방법
EP15725880.7A EP3129423B1 (fr) 2014-04-11 2015-04-09 Système et procédé de production de polycarbonates par fusion de poids moléculaires différents

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WO2017093974A1 (fr) * 2015-12-03 2017-06-08 Sabic Global Technologies B.V. Procédé de récupération d'un alcool aromatique à partir d'une polymérisation en masse fondue et système pour sa récupération
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US20190367669A1 (en) * 2016-10-12 2019-12-05 EPC Engineering & Technologies GmbH Catalyst system
EP3581605A1 (fr) 2018-06-14 2019-12-18 Covestro Deutschland AG Procédé de commande de fonte pour la production simultanée d'au moins deux polycarbonates différents dans une installation de production
US11879035B2 (en) 2018-10-11 2024-01-23 Sabic Global Technologies B.V. Polycarbonate
US12077635B2 (en) 2018-10-11 2024-09-03 Sabic Global Technologies B.V. Method for the manufacture of polycarbonate

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US12084542B2 (en) * 2018-12-05 2024-09-10 Sabic Global Technologies B.V. Polycarbonate compositions with improved oxidation stability and methods of manufacturing the same

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US10106648B2 (en) 2014-11-19 2018-10-23 Sabic Global Technologies B.V. Method of polymerizing end-capped polycarbonate and end-capped polycarbonates derived therefrom
WO2016079706A1 (fr) * 2014-11-19 2016-05-26 Sabic Global Technologies B.V. Procédé de polymérisation de polycarbonate à extrémité coiffée et polycarbonates à extrémité coiffée ainsi dérivés
CN108290820B (zh) * 2015-12-03 2021-10-01 沙特基础工业全球技术有限公司 从熔融聚合中回收芳香族醇的方法以及用于回收其的系统
KR20180088676A (ko) * 2015-12-03 2018-08-06 사빅 글로벌 테크놀러지스 비.브이. 방향족 알코올을 용융 중합으로부터 회수하는 방법 및 이를 회수하기 위한 시스템
CN108290820A (zh) * 2015-12-03 2018-07-17 沙特基础工业全球技术有限公司 从熔融聚合中回收芳香族醇的方法以及用于回收其的系统
WO2017093974A1 (fr) * 2015-12-03 2017-06-08 Sabic Global Technologies B.V. Procédé de récupération d'un alcool aromatique à partir d'une polymérisation en masse fondue et système pour sa récupération
KR102472219B1 (ko) 2015-12-03 2022-11-29 사빅 글로벌 테크놀러지스 비.브이. 방향족 알코올을 용융 중합으로부터 회수하는 방법 및 이를 회수하기 위한 시스템
US20190367669A1 (en) * 2016-10-12 2019-12-05 EPC Engineering & Technologies GmbH Catalyst system
US11945909B2 (en) * 2016-10-12 2024-04-02 EPC Engineering & Technologies GmbH Process for preparing polycarbonates using a catalyst system having a quarternary nitrogen compond and a quarternary phosphorous compound
WO2019069207A1 (fr) * 2017-10-05 2019-04-11 Sabic Global Technologies B.V. Procédé amélioré de modification d'un polycarbonate pendant une polymérisation par fusion
EP3581605A1 (fr) 2018-06-14 2019-12-18 Covestro Deutschland AG Procédé de commande de fonte pour la production simultanée d'au moins deux polycarbonates différents dans une installation de production
WO2019238419A1 (fr) 2018-06-14 2019-12-19 Covestro Deutschland Ag Procédé de transestérification en fusion pour la fabrication simultanée d'au moins deux polycarbonates de types différents dans une installation de production
US11879035B2 (en) 2018-10-11 2024-01-23 Sabic Global Technologies B.V. Polycarbonate
US12077635B2 (en) 2018-10-11 2024-09-03 Sabic Global Technologies B.V. Method for the manufacture of polycarbonate

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US20170015784A1 (en) 2017-01-19
CN106068295B (zh) 2018-09-25
EP3129423A1 (fr) 2017-02-15
KR20160143696A (ko) 2016-12-14
EP3129423B1 (fr) 2022-05-25
KR102165343B1 (ko) 2020-10-14
CN106068295A (zh) 2016-11-02

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